Photovoltaic devices are known in the art (e.g., see U.S. Patent Document Nos. 2004/0261841, 2006/0180200, U.S. Pat. Nos. 6,784,361, 6,288,325, 6,613,603, and 6,123,824, the disclosures of which are hereby incorporated herein by reference). Examples of photovoltaic devices include CIGS (Cu(In, Ga)(Se, S)2), CIS (CuInSe2), and a-Si (amorphous silicon) solar cells. The CIGS and CIS films are conductive semiconductor compounds, and these stoichiometries are approximations.
Generally speaking, CIGS and CIS type photovoltaic devices include, from the front or light incident side moving rearwardly, a front substrate of a material such as glass, a front electrode comprising a transparent conductive layer such as a TCO (transparent conductive oxide), a light absorption semiconductor film (e.g., CIGS and/or CIS film), a rear electrode, and a rear substrate of a material such as glass. Sometimes an adhesive is provided between the front substrate and the front electrode, and it is also possible for window layer(s) (e.g., of or including CdS, ZnO, or the like) to be provided. Photovoltaic power is generated when light incident from the front side of the device passes through the front electrode and is absorbed by the light absorption semiconductor film as is known in the art.
A metal such as Mo (molybdenum) may be used as the rear electrode (bottom contact) of a photovoltaic device, such as a CIS solar cell. In certain instances, the Mo may be sputter-deposited onto a soda or soda-lime-silica rear glass substrate of the photovoltaic device. However, Mo rear electrodes suffer from the problem of delamination from the rear substrate.
Rear electrodes (e.g., Mo rear electrodes) preferably have low stress, high conductivity, and good adhesion to the rear substrate (e.g., glass substrate). In order to provide this combination of features, oxygen is introduced into the Mo rear electrode at the initial stage of deposition of the rear electrode on the substrate or otherwise in certain example embodiments of this invention. The application of the oxygen to the Mo rear electrode reduces the overall stress of the rear electrode and at the same time promotes adhesion of the rear electrode to the glass soda or soda lime silica glass substrate.
In certain example embodiments of this invention, there is provided a method of making the rear electrode for CIS and/or CIGS photovoltaic (e.g., solar cell) devices using magnetron sputter-deposition of molybdenum (Mo) in a multi-layer configuration. In certain example embodiments, nitrogen and/or hydrogen (e.g., H2) gas(es) are used as additives to the sputtering gas (e.g., argon) to reduce stress of the coating, enhance its resistance to the selenization during the downstream device processing, and promote beneficial sodium migration from the soda-lime rear glass substrate to the semiconductor film of the device.
In certain example embodiments, there is provided a method of making a rear electrode structure for a photovoltaic device, the method comprising: providing a glass substrate; depositing a conductive electrode comprising Mo (molybdenum) on the glass substrate; and wherein said depositing the conductive electrode comprising Mo (molybdenum) comprises sputtering at least one target comprising Mo (metallic Mo or a MoOx ceramic in example embodiments) in an atmosphere including (i) an inert gas such as argon or the like, and (ii) from about 0.1 to 10% nitrogen and/or hydrogen gas.
In certain example embodiments of this invention, there is provided a method of making a rear electrode structure for a photovoltaic device, the method comprising: providing a glass substrate; depositing a conductive electrode comprising Mo (molybdenum) on the glass substrate; and wherein said depositing the conductive electrode comprising Mo (molybdenum) comprises sputtering at least one ceramic target comprising MoOx and at least one metallic target comprising Mo in depositing the conductive electrode.
In certain example embodiments of this invention, there is provided a method of making a rear electrode structure for a photovoltaic device, the method comprising: providing a substrate (glass or any other suitable material); depositing a conductive electrode comprising a metal (M) on the substrate; and wherein said depositing the conductive electrode comprises sputtering at least one ceramic target comprising MOx and at least one metallic target comprising M in depositing the conductive electrode. The metal M may be Mo or any other suitable metal.
In other example embodiments of this invention, there is provided a method of making a rear electrode structure for a photovoltaic device, the method comprising: providing a glass substrate; depositing a conductive electrode comprising Mo (molybdenum) on the glass substrate; and wherein said depositing the conductive electrode comprising Mo (molybdenum) comprises sputtering at least one ceramic target comprising MoOx, where x is less than or equal to 0.1.
In other example embodiments of this invention, there is provided a photovoltaic device comprising: a front substrate; a front substantially transparent conductive electrode; an absorber semiconductor film; a conductive and reflective rear electrode; a rear glass substrate that supports at least the rear electrode; and wherein the rear electrode comprises a first layer or layer portion comprising an oxide of Mo and a second conductive layer or layer portion comprising substantially metallic Mo provided on the rear glass substrate over at least the first layer, so that the first layer or layer portion comprising the oxide of Mo is located between the rear glass substrate and the second layer or layer portion comprising substantially metallic Mo.
In certain example embodiments, the rear electrode is formed in a manner so that its major surface to be closest to the light absorption semiconductor film of the photovoltaic device is textured (roughened) in a substantially controlled and desired manner. In certain example embodiments, the interior surface of the rear glass substrate is textured (roughened) via acid etching, ion beam treatment, or the like. Then, the Mo inclusive rear electrode is formed on the textured surface of the rear glass substrate in a manner so that the major surface of the rear electrode to be closest to the light absorption semiconductor film is also textured. In certain example embodiments, the textured major surface of the rear electrode to be closest to the light absorption semiconductor film may be substantially conformal to the textured surface of the rear glass substrate.
The embodiments where the rear substrate is textured may or may not be used in combination with the embodiments where the rear electrode is oxidation graded, in different example embodiments of this invention.
The textured interior surface of the rear electrode is advantageous in several example respects. The textured surface of the rear electrode improves adhesion between the rear electrode and the semiconductor film. Moreover, the textured surface of the rear electrode allows the rear electrode to act as a scattering back electrode thereby permitting it to reflect incident light more effectively and efficiently into the light absorption semiconductor film. This can allow one of both of: improved efficiency of the photovoltaic device, and/or reduced thickness of the light absorption semiconductor film without sacrificing solar efficiency. In certain example embodiments, after the rear electrode has been formed on the rear glass substrate, the major surface of the rear electrode to be closest to the light absorption semiconductor film may be textured via one or more of ion beam treatment, plasma exposure, and/or a wet chemical etch such as HCl, nitric acid, acetic acid or a combination thereof. This post-deposition texturing (roughening) of the rear electrode surface may, or may not, be used in combination with embodiments where the rear glass substrate is textured. Thus, when the rear electrode is textured (roughened) after the deposition thereof, the rear glass substrate may or may not be textured. The textured rear glass substrate and/or textured rear electrode (which also functions as a reflector) may be used in a photovoltaic device (e.g., CIS or CIGS solar cell) where an active semiconductor film is provided between the rear electrode/reflector and a front electrode(s).